US4092342A - Method for recovering alkylaluminum chlorides - Google Patents
Method for recovering alkylaluminum chlorides Download PDFInfo
- Publication number
- US4092342A US4092342A US05/772,578 US77257877A US4092342A US 4092342 A US4092342 A US 4092342A US 77257877 A US77257877 A US 77257877A US 4092342 A US4092342 A US 4092342A
- Authority
- US
- United States
- Prior art keywords
- chloride
- mixture
- zinc
- dialkylaluminum
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- -1 alkylaluminum chlorides Chemical class 0.000 title description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 40
- 239000011701 zinc Substances 0.000 claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 12
- 150000003752 zinc compounds Chemical class 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 239000000460 chlorine Substances 0.000 description 18
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 16
- 238000004821 distillation Methods 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 8
- 235000005074 zinc chloride Nutrition 0.000 description 8
- 239000011592 zinc chloride Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000007700 distillative separation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/064—Aluminium compounds with C-aluminium linkage compounds with an Al-Halogen linkage
Definitions
- the present invention relates to a method for the recovery of dialkylaluminum chloride and/or alkylaluminum dichloride having 1 to 6 carbon atoms in the alkyl groups and having a zinc concentration of less than 200 parts per million from a mixture of dialkylaluminum chloride and soluble zinc compounds, which mixture may also contain trialkylaluminum.
- German patent publication DAS No. 1,159,447 describes a method for preparing dialkylzinc from trialkylaluminum and zinc chloride. The reaction takes place according to equation I:
- dialkylaluminum chloride is produced as a by-product. It is recommended to separate the dialkylzinc and the dialkylaluminum chloride by distillation. Although distillative separation is, basically, superior to all other methods, for example to those involving separation by selective complex formation, it nevertheless shows the disadvantage that it is practically impossible to recover a dialkylaluminum chloride having a concentration of less than 200 ppm of zinc, as is required for many uses to which the product is put. This is particularly the case when the product is used as a catalyst component, for example for the diethylaluminum chloride which appears as a by-product in the preparation of diethylzinc from triethylaluminum and zinc chloride.
- dialkylaluminum chlorides having a zinc concentration of 200 ppm or less can be obtained from a mixture of dialkylaluminum chlorides and soluble zinc compounds such as is formed in the preparation of dialkylzinc according to DAS No. 1,159,447 or No. 1,493,222, if the mixture is strongly heated in order selectively to pyrolyze the zinc-containing compounds and then the dialkylaluminum chloride is distilled off in higher purity.
- the object of the present invention it is to avoid these disadvantages, to find a method which reduces the zinc content of alkylaluminum chlorides produced in the preparation of dialkylzinc, and in this way to obtain highly pure alkylaluminum chlorides which will meet the purity requirements for further technical uses, for example for the preparation of catalysts.
- the object has been attained according to the present invention, in which a mixture of dialkylaluminum chloride and soluble zinc compounds, possibly also containing trialkylaluminum, is reacted with aluminum chloride under an inert atmosphere at temperatures up to about 150° C. and, subsequently, dialkylaluminum chloride and/or alkylaluminum dichloride are distilled off.
- dialkylzinc is converted into a chlorine-containing zinc compound, for example into zinc chloride according to equation IV:
- the process can be so directed according to the amount of aluminum chloride which is added that one can, according to choice, obtain either dialkylaluminum chloride or alkylaluminum dichloride or mixtures of both.
- the distillative removal of the dialkylaluminum chloride and/or of the alkylaluminum dichloride can take place according to the present invention without a column.
- the help of a column may be suitable.
- the distillation must be performed under an inert atmosphere, suitably under reduced pressure, so that the head temperature does not exceed about 150° C.
- Alkylaluminum dichlorides for example ethylaluminum dichloride, and mixtures of dialkylaluminum chlorides and alkylaluminum dichlorides, for example ethylaluminum sesquichloride, are compounds which are sought as much as the dialkylaluminum chlorides, for example diethylaluminum chloride.
- alkylaluminum dichlorides can also be easily converted to dialkylaluminum chlorides by comproportionation with trialkylaluminum.
- the filtered distillation residue was a colorless clear liquid which in large part comprised diethylaluminum chloride and, in addition to 19.7% of Al and 27.7% of Cl, still contained 3.1% of soluble Zn. 83.5 g of this material were added to a 250 ml 3-necked flask equipped with a stirrer, a thermometer, and a reflux condenser. The entire system was kept under nitrogen at atmospheric pressure. 93.5 g of aluminum chloride were added to this material and the reaction mixture was heated.
- a diethylaluminum chloride was chosen which, in addition to 20.7% of Al and 27.5% of Cl, still contained 3.0% of soluble Zn.
- 89 g of this material were, as described in Example 1, reacted with 92.5 g of aluminum chloride. After the aluminum chloride had dissolved, the reaction mixture was vacuum distilled as described in Example 1. At a head temperature of 93° C. to 101° C., 161 g of colorless and clear distillate passed over. This corresponded to a yield of 88.7%. The distillate showed the following analysis:
- diethylaluminum chloride having a content of about 8% of triethylaluminum was chosen, which product still contained 2.5% of soluble zinc in addition to 20.9% of Al and 25.0% of Cl.
- 100 g of this material were added to a 500 ml 3-necked flask equipped with a stirrer, a thermometer, and a reflux condenser. The entire system was held under nitrogen at atmospheric pressure. This material was heated with stirring and, at 50° C. to 60° C., 128.9 g of aluminum chloride were added portion-wise. After the aluminum chloride had reacted, the reaction mixture was vacuum distilled as described in Example 1. At a head temperature of 94° C. to 103° C., 211.5 g of colorless and clear distillate passed over. This corresponds to a yield of 92.4%. The distillate showed the following analysis:
- a diisobutylaluminum chloride was chosen which, in addition to 14.5% Al and 19.2% Cl, still contained 1.5% of soluble Zn. 100 g of this material were, as described in Example 3, reacted with 81.1 g of aluminum chloride. The reaction mixture was distilled twice through a Claisen attachment, first at a reduced pressure of 10 mm Hg, then at a pressure of 0.1 mm Hg.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DT2628191 | 1976-06-23 | ||
| DE2628191A DE2628191C2 (de) | 1976-06-23 | 1976-06-23 | Verfahren zur Gewinnung von Alkylaluminiumchloriden |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4092342A true US4092342A (en) | 1978-05-30 |
Family
ID=5981258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/772,578 Expired - Lifetime US4092342A (en) | 1976-06-23 | 1977-02-28 | Method for recovering alkylaluminum chlorides |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4092342A (fr) |
| BE (1) | BE856038A (fr) |
| DE (1) | DE2628191C2 (fr) |
| IT (1) | IT1080672B (fr) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670571A (en) * | 1985-10-15 | 1987-06-02 | Texas Alkyls, Inc. | Method for recovery of alkylaluminum halides |
| US4732992A (en) * | 1986-12-22 | 1988-03-22 | Stauffer Chemical Company | Method for recovery of alkylaluminum halides |
| WO2009133929A1 (fr) | 2008-04-30 | 2009-11-05 | 日本アルキルアルミ株式会社 | Procédé de fabrication de dialkyle zinc et de monohalogénure de dialkyle aluminium |
| WO2010055704A1 (fr) | 2008-11-12 | 2010-05-20 | 日本アルキルアルミ株式会社 | Procédé pour la production de monohalogénure de dialkylaluminium |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2270292A (en) * | 1938-03-21 | 1942-01-20 | Universal Oil Prod Co | Process for producing a mono-hydrocarbon aluminum dihalide |
| US2996529A (en) * | 1955-12-21 | 1961-08-15 | Stamicarbon | Preparation of diethyl aluminum chloride |
| US3124604A (en) * | 1956-02-21 | 1964-03-10 | New organic zinc compounds and a proc- | |
| US3946058A (en) * | 1974-06-17 | 1976-03-23 | Texas Alkyls, Inc. | Process for recovering of dialkylaluminum halide from mixtures containing soluble zinc |
-
1976
- 1976-06-23 DE DE2628191A patent/DE2628191C2/de not_active Expired
-
1977
- 1977-02-28 US US05/772,578 patent/US4092342A/en not_active Expired - Lifetime
- 1977-06-23 BE BE178718A patent/BE856038A/fr not_active IP Right Cessation
- 1977-06-23 IT IT24995/77A patent/IT1080672B/it active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2270292A (en) * | 1938-03-21 | 1942-01-20 | Universal Oil Prod Co | Process for producing a mono-hydrocarbon aluminum dihalide |
| US2996529A (en) * | 1955-12-21 | 1961-08-15 | Stamicarbon | Preparation of diethyl aluminum chloride |
| US3124604A (en) * | 1956-02-21 | 1964-03-10 | New organic zinc compounds and a proc- | |
| US3946058A (en) * | 1974-06-17 | 1976-03-23 | Texas Alkyls, Inc. | Process for recovering of dialkylaluminum halide from mixtures containing soluble zinc |
Non-Patent Citations (1)
| Title |
|---|
| Zakharkin et al., Zh. Obsh. Khim. 31, 3662-3665 (1961). * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4670571A (en) * | 1985-10-15 | 1987-06-02 | Texas Alkyls, Inc. | Method for recovery of alkylaluminum halides |
| EP0218994B1 (fr) * | 1985-10-15 | 1992-04-01 | Texas Alkyls Inc. | Méthode de récupération d'halogénures d'alkylaluminium |
| US4732992A (en) * | 1986-12-22 | 1988-03-22 | Stauffer Chemical Company | Method for recovery of alkylaluminum halides |
| EP0272560B1 (fr) * | 1986-12-22 | 1992-04-01 | Texas Alkyls, Inc. | Méthode de récupération d'alkyl-aluminium-halogénures |
| WO2009133929A1 (fr) | 2008-04-30 | 2009-11-05 | 日本アルキルアルミ株式会社 | Procédé de fabrication de dialkyle zinc et de monohalogénure de dialkyle aluminium |
| US20110054206A1 (en) * | 2008-04-30 | 2011-03-03 | Nippon Aluminum Alkyls, Ltd. | Method for manufacturing dialkylzinc and dialkylaluminum monohalide |
| CN102015730A (zh) * | 2008-04-30 | 2011-04-13 | 日本烷基铝株式会社 | 用于制备二烷基锌和一卤化二烷基铝的方法 |
| US8236981B2 (en) | 2008-04-30 | 2012-08-07 | Nippon Aluminum Alkyls, Ltd. | Method for manufacturing dialkylzinc and dialkylaluminum monohalide |
| WO2010055704A1 (fr) | 2008-11-12 | 2010-05-20 | 日本アルキルアルミ株式会社 | Procédé pour la production de monohalogénure de dialkylaluminium |
| US20110021800A1 (en) * | 2008-11-12 | 2011-01-27 | Nippon Aluminum Alkyls, Ltd. | Method for manufacturing dialkylaluminum monohalide |
| US8110694B2 (en) | 2008-11-12 | 2012-02-07 | Nippon Aluminum Alkyls, Ltd. | Method for manufacturing dialkylaluminum monohalide |
| CN101868466B (zh) * | 2008-11-12 | 2013-01-16 | 日本烷基铝株式会社 | 用于制备一卤化二烷基铝的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2628191A1 (de) | 1978-01-05 |
| IT1080672B (it) | 1985-05-16 |
| BE856038A (fr) | 1977-12-23 |
| DE2628191C2 (de) | 1984-10-04 |
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